TTL740
Dr. Mangala Joshi
Course Coordinator
Lecture 8
Surface Electron oscillation
There is electron delocalization in metals or sea of electrons –
configuration of electron orbitals
Electron delocalization
A surface plasmon is
characterized as a surface
charge density wave at a
metal surface.
` Surface Plasmons are collective oscillations of
valence electrons associated with surface atom
` - insignificant in spectra of bulk metals
` ‐ important in nanosized particles of certain metals
like gold and silver
` High Surface area to volume ratio
` Surface Plasmon resonance is a physical
phenomenon of certain metals where upon
excitation by incident light at the same
frequency as surface electron oscillation
(plasmons), a specific and unique resonance
pattern is observed.
Simply, a thin film of metal like gold can absorb a laser light and
produce electron waves or oscillations of the delocalized electron
cloud. This occurs only at very specific angle and only at the thin
metal- dielectric interface ( water or air).
What is Surface Plasmon ?
Surface plasmons also known as surface plasmon
polaritons, are surface electromagnetic waves that
propagate in a direction parallel to the metal /
dielectric i.e water /air ( or metal / vacuum)
interface.
Since wave is on boundary of the metal and the
external medium (air or water); these oscillations are
very sensitive to any change of this boundary such as
adsorption of molecules on surface of metal
` The excitation of surface plasmons by light is
denoted as surface plasmon resonance (SPR) for
planar surfaces or localized surface plasmon
resonance (LSPR) for nanometer sized metallic
clusters.
` In order to excite surface plasmons in a resonant
manner, one can use an electron or light beam
(visible and infrared are typical). The incoming
beam has to match its impulse to that of the
plasmon.
Silver and Gold particles have different
colors depending on size and shape
Surface Plasmon Resonance
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` Electrons from the outer valence orbitals are susceptible to
manipulation, especially when the orbital is not completely
filled.
` Electromagnetic radiation (EMR) carries bundles of energy
called photons and is able to impart some of its energy on
matter,
` The wave‐particle duality asserts that electrons have
properties of both waves and particles.
` When the frequency of the incident EMR matches that of
surface electrons oscillations on thin conducting metals, an
amplification of this frequency will be propagated along the
overlapping electron orbitals.
` This transfer of energy is referred to as evanescent‐wave
coupling, and it is necessary for SPR to occur.
` Total internal Reflection
` Light has to be p-polarized -parallel to the
plane of incidence or it will not be able to
excite surface electrons
Total Internal Reflection.
Based on Snell’s Law, light is refracted as
is passes through different mediums,
illustrated here as air and water.
The refractive index for air is 1.0003 and
for water is 1.333.
b) Reflection of polarized light. Only light
waves that oscillate in the same plane as
the contact surface will be able to impart
their energy on surface electrons.
TIR occurs when the angle of incidence is greater than
the critical angle.
` Evanescent waves are formed when
EMR undergoes total internal
reflection at the boundary between
two materials.
The wave vector of
light can be tuned to
equate the plasmon
wave vector by
varying either the
angle of incidence or
the wavelength of
light
Surface plasmon resonance in nanoparticles
‐Suspension or sols containing nanoparticles give rise to
intense colour due to localized surface plasmon
oscillations.
‐ Nanoparticles or nanowires of noble metals exhibit strong
adsorption bands in UV‐Visible light regime that are not
present in the bulk metal
‐Typical metals that support surface plasmons are silver
and gold but metals such as copper, titanium or chromium
are also applicable
(a) Optical spectroscopy measurements of individual silver nanoparticles,
(b) (b) (top) an electronic camera (Nikon Coolpix 950) color image of a typical
sample of silver nanoparticles as viewed under the darkfield microscope,
(c) (bottom) a bright field TEM image of the same collection of silver
nanoparticles
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` The physical origin of the strong light absorption by noble metal
nanoparticles is the coherent oscillation of the conduction band
electrons (surface plasmon oscillation) induced by interaction
with an electromagnetic field.
` Mie first described theoretically the strong absorption band in
the visible region by spherical gold nanoparticles
` The resonance frequencies as well as the width of the plasmon
absorption band depend on the nanoparticles size and many
theories have been developed to explain the observed
experimental behavior .
` In the case of gold nanorod the plasmon resonance splits into
two modes: one longitudinal mode parallel to the long axis of
the rod and a transverse mode perpendicular to the first.
R is aspect ratio of nanorods
` The spectrum of gold nanospheres (20nm in diameter) shows the characteristic strong
absorption band at ≈522nm that is assigned to the dipole resonance of the gold nanospheres.
` Very small nanoparticles(<2 nm) as well as bulk gold do not show this absorption.
` On the other hand PA spectrum of gold nanorods is characterized by two bands, the short
wavelength band is located at about 522nm and is attributed to the transverse SPR.
` The longer wavelength band (698 nm) is attributed to the longitudinal SPR due to nanorods.
The SPR resonance pattern is extremely sensitive to any
changes in environment just outside the metal film
( refractive index changes)
` Angle of the reflection minimum (absorption maximum) is
measured. This angle changes in the order of 0.1° during thin
(about nm thickness) film adsorption.
` In other cases the changes in the absorption wavelength is
followed.
` The mechanism of detection is based on that the adsorbing
molecules cause changes in the local index of refraction,
changing the resonance conditions of the surface plasmon
waves.
` Phenomenon is basis of many tools for
measuring adsorption of material on planar
metal (Au / Ag) surfaces or surface of
Nanoparticles ( metal surface and
conjugated ligands)
- Colour based biosensors
- Lab-on-a-chip sensors
SPR reflectivity measurements can be used to
detect molecular adsorption, such as polymers,
DNA or proteins, etc.